Treatment of aliphatic hydrocarbons



G. w. HowLETT 1,826,787

TREATMENT 0F ALIPHATIC. HYDROCARBONS i Filed Feb, 24, 1923 Y 4 .v 0 ma. A

, A kwww A Y b A f f Y .n f,

oct. 13, 1.931'.

Patented oa. 13,1931

UNITED STATES vPA-'IEN'riolffl-lci-z y GRAYLE' W. EOWLETT, Ol' TOLEDO, OHIO,

ASSIG'IN'OIB 0F ON-HALF TO ROBERT M.. CORI', F MAUMEE, OHIO maremma or Lunario rrrnnocannons- Application med February 24, 1923. Serial JNO. 630,887.l

My invention relates to methods of treating aliphatic hydrocarbons and more particularly to the treatment of petroleumyoils, their distillates and residues. My invention has for its object the production of the more desirable lower boiling compounds rom the less desired higher boiling petroleum hydrocarbons.

In achieving my object, discovery that a non-metallic halogen derivative acts upon aliphatichydrocarbons present in petroleum oils mediate compounds formed therefrom, t0

A form lower boiling compounds. Various nonmetallic halogen derivatives are more or less eiective in achieving my purpose, among which may be mentioned aromatic or al1- I phatic acidchlorides, acetyl bromide, phos- 1 halide may be ess possible,

' connection l an apparatus such p gene, etc., but they are costly and not readily available, therefore, the substance which I prefer to use, because of its cheapness and availability, is analkyl halide.

introduced into the oil as such, or reagents may be used which will produce the alkyl halide within the oil under treatment. I prefer the latter method, and the substances which I have found eflicient for the purpose, and most readily available commercially, are the monohydric alcohols, sodium chloride, and sulphuric acid. The sodium chloride and sulphuric acid react to form hydrochloric acid, which, in turn, interacts with an alcohol such as methanolgto form methyl chloride. v There are many modifications of my proctreatcd and the materials available for treatment, and I shall not attempt to stateall of the various ways in which the rocess may be modiiied, but will indicate a ew of them in 1n preferred process.

the preferred form of the rocess, I use as is shown 1n the accomdrawing, to which reference is had in the ollowing description of the process.

e Oil to be treated is placed in a lstill 1,

r having therein agitating means 2,-driven` by wormgfgearmg 3; 50v

The materials are introducedinto the through anmlet tank 6 contains one of the alky I make use of my.

their distillates, or inter" @pipe The alkyl according to the substances to be g with the following'description of treatment.A In such cases,

hip@ 4,

the higher boiling hydrocarbons being directed into the pipe 4 from the pipe 5. A l halide forming rea vents 'such as methanol. This mater1al may be introduced into the still, with the heavier hydrocarbons; but I prefer to intraduce it'into the still with the other chemicalswith whichit may be mixed, in a mixer @provided or'this purpose. The mixer 7 islequlpped with agitating meansS driven by "gear train 9. The materials are passed vfrom the mixer 7 to the inlet. pipe 4 through a plpe 10, into which they may pass through 11,-controlled by a valve 12 or through a pipe 13, valve 14,' circulating pump .15,

pipe 16 and valve 17. The lmethanol, if desired, may be passed from the receptacle 6 through pipes 18 and 19, to the `A suitable furnace, as illustrated at 27, surhopper 20. and sodium chloride may be introduced into.

24 `is passed through rounds the still 1. vThe still vapors may proceed through this pipe 31, and `expans1pn valve 32,. to the chamber 33 and if desired the reiiux coil 29 may be used by allowing the vapors to pass through the pipe 28, whereby the vapors ma be condensed and the condensate' returned to the still and any fixe ases returned to the still through pump 57 and line 58. l y

From the chamberV 33, the compounds, which have not been changed to the desired lower boiling compounds, are passed bac through the ipe 34 and valve 35, into the mixing cham er 7,"rirom'whence they may be returned to the still 1. Inl some cases, this product, which is' condensed in chamber 33, may be collected and used without further v the valve 35 1s closed and this condensed product is pass I off through the `pipe 36 and valve 37. -If 1t 1S keu necessar' to remove foreign matter,lsuch as through the separator 48 and directed to the hopper 20, or passed through the outlet 49 to storage. The vapors, which are not condensed in chamber 33, pass out through pipe suitable means to a gas storage receptacle.

l(not shown), from which receptacle the gas may bedistributed for fuel purposes, if desired, or used as a component in the preparation of treating materlal. Anoutlet device 50 is provided for removal of deposits Vfrom the still, .or for the removal of residual oil i therefrom. v

This apparatus is adapted to intermittent or continuous'operationof the process. If the oil is to be treated intermittently the entire amount to be treated is charged into the still and the reagents added vcontinuously on intermittently or both.

In treating topped Penns lva'nia crude I have found it desirable to adrd about 5%, by volume, of methanoland 2%, by weight,- of sodium chloride to the charge of oil in the still. The chargeis then broug` t to a retlux, ing temperature of about y600 and retlux'ed for one hour with the gradual addition ofsulphuric acid.. The `total amount of sulphuric acid found advisable for such treatment is approximately 1%, by weight, of the original charge of oil, the sulphuric acid, lhowever, being added at such'a rate as to avoid the formation of an excess of hydrochloric converted to lower boiling compounds, which are recovered by distillationl It is found that about 7% of the charge of topped oil has been changed to gasoline, with an end point of 400 F., while about 70% ofthe charge has been changed to kerosene distilling under 590 F' The kerosene may be treated in a similar manner, resulting in a total yield ofY about 651/2% of the original crude as water white gasoline, including that `'gasoline first removedv by top-ping, and about 22%. as kerosene, of .8 specific ravity and 590 F. end point. The residue, a er such treatment,

contains about 8% of the original charge in the form of oil suitable for burning ur poses mixed withj sodium. sulphate, car on, etc. These gures'are, of course, given as merely an example of what may be accomf,

plished in applfy'ing this process, as the time and manner o pressure, etc., may be varied as desired, with different materials and in accordance with "the end products desired. It should be understood that conversion takes place' at-many temperatures between that of the boiling treatment, degrees of heai:,'

lprefer to conduct the method con" tinuously wherein the materials are being constantly added to the contents of the still, as theI lower boiling hydrocarbons are being distilled off. The qualities of the material which I have found advisable to employ are such, that, with a ixed distillation rate, they are continuously replenished in such manner that their quantities and proportions remain practically constant, notwithstanding the removalv of materials byd distillation and as residues or gas.

Essentiall the same apparatus, may be used for various modifications of the process. If desired, an alkyl halide may be introduced directly into the charge, instead of introducing. the' chemicals which will ultimately form an valkyl halide. As for example, methyl chloride may be secured from any desired source and passed into the still. The methyl chloride may be iormed in any suitable generator such as the mixer 7 and passed to the still through pipes 10 and l1 andvalve12.' Methyl alcohol and sodium chloride may be treated with sulphuric acid in Aa receptacle and the resultant methyl chloride directed into the still.

I have found that a charge ofr kerosene, heated to about 500 F.. and refluXed for one hour, with the) introduction of methyl chloride continuously to a total amount of about 1% by weight of the charge of oil used, acld. A iarge proportion of the charge 1s available, is the treatment of methane with chlorine, whereb methyl ,chloride and hydrochloric aci are produced. I have found considerable of the alkyl halide is recovered in the .tail gases and that hydrochloric is produced in the reaction.

Ifpreferto operate at substantially atmospheric pressures, valthough the process may be-'usedwith` higher pressures, or pressures below atmospheric, and the treatment may take place while the materials are `in the gaseous or vaporous state. As shown in the drawing, a by-pass around the valve 32, havling a pump 53, is controlledby valves 51A and 52. The by-pass.f and the vapor line.

31, form the intake line of the compressor member 53, through which vapors from the st lll 1 are drawn, and ldirected into the compressor. The'nonemetallic halogen derivative, used in't'reatin the oil vapors, is drawn from the generator throughthe line 59 into a non-metallic halogenderivative,

member.- Varlous other modifications of the mannerv the vapor line 31, the valve 32 being closed.

This mixture of oil and treating materials, in

is subjected to compression v the vapor phase, in the member 53. conversion being assisted by compression and the esulting products are expanded to any desir d pressure in .the expansion chamber 33. Where pressures above atmospheric are maintained on the still, the chamber 33 may act as aniexpanslon As will be seen from the foregoing, my invention relates broadly to the treatment of the higher boiling aliphatic hydrocarbons, with referaably an alkyl halide such as methyl c lorlde. The methyl haloid, maybe introduced directly, as such, or formed within the body of the oil under treatment, or used in contact with the vapors of such oils, as desired; however I prefer 3'0 to form the alkyl halide in' the nascent state,

and preferably bythe reaction of a monohydric alcohol, either present, introduced'eor produced in the oil, with a halogen acid such as hydrochloric acid. The hydrochloric acid, likewise, may be introduced as such, or formed in any' desirablemanner within the oil, as by the treatment of sodium chlorlde with sulphuric acid, or by the action of a hydrogen containing gas such as methane, with a halogen such-as chlorine, or by the action of water on h anhydrous metallic chloride, or in any other. manner readily occur to those skilled in the art. Apparently the alkyl group disappearsin the reaction', combining with the higher boiling aliphatic hydrocarbons, or intermediate compounds ormed therefrom, to produce anunstable compound.- Through a molecular rearrangement induced by heatdower boiling [form an alkyl halide,

aliphatic compounds vare formed. The reagents -may ly, when introduced s o as to form the alkyl halide within the oil being treated.

Where gases of the methane series are present in the oil under treatment, or are'jformed during the process, or are available in a cheap form, it is sometimes advisable to treat these gases with a halogen, such as chlorine, to and a halogen acid such as hydrochloric acid; the halogen acid thus formed may be employed to treat an alkyl derivative of benzene, such as xylene, or an alcohol, such as methyl alcohol, to form an alkyl halide, such as methyl chloride.

In general, it will be seen that the process can be varied by the'use of diferent chemi- .obj ective of the chloride, or other non-metallic` which will be used somewhat more eilic'ientcals introduced in dilerent ways, and treated under varying degrees of pressure and heat, and which will form alkyl halide accordance with the adaptability of the variousmaterials and the particular purpose 7 ofthe treatment and without, necessarily, the

aid of metallic halogen compounds, although metallic halogens may be used in the processes involving the use of my invention without departing from the spirit thereof, thea invention being to produce lower boiling hydrocarbons by the use of non-metallic halogen derivatives. I therefore do'not wish to be conned to any of the processes set forth above as they have been 8 selected and described merely as illustrations of the various processes wherein my invention is utilized.

In the appended claims IV use the term petroleum hydrocarbons andv I wish it understood that by the terms I include crude petroleum oils, their distillates, intermediate compounds and residues.

I claim:

1. The process consisting in treating heated petroleum hydrocarbons with anon-metallic halogen derivative contaning an alkyl radical and without the 'aid of metallic halogen derivatives and thereby producing unstable compounds and heating the mixture Zat a temperature suitable for conversion ac- -tion of' the alkyl halide to produce the lower f boiling compounds.

2. The process consisting in treating heatedpetroleum hydrocarbons with an -alkyl Y halide and without the aid of me llic halogen derivatives and thereby pro ucing unstable compounds and heating the mixture at a temperature suitable for conversion acion of the alkyl halide to produce the lower Y boiling compounds.

3. The process consisting in treating heated Apetroleum hydrocarbons with aunethyl halide and without the aid of metallic halogen derivatives and'thereby producing un- 'stable compounds andheating the mixture at a temperature suitable vfor conversion action of the halide to produce ing compounds. Q Y

4. The process consisting in treating heated petroleum hydrocarbons with methyl chloride and without the aid of .metallic the lower boilhalogen derivatives and thereby producing-' unstable compounds and heating the mixture atI a temperature suitable `for conversion .action of the chloride to'produce the lower n boiling compounds.

" 5. The process consistingin treating pe troleum hydrocarbonswwith a non-metallic halogen derivative contaning an alkyl radical and without the aid of halogen metallic derivatives and thereby produce unstable compounds, heating the mixture at a temperature suitable for conversion action of the halide to produce the lower boiling comlll .lill

pounds, distilling o the lower boilin "compounds-as formed, and returning for urther treatment the higher boiling of the distillates i hile the mixture is subjected to a conversion temperature. n

6. The process consisting in treating petroleum hydrocarbons with an alkylhalldeand Without the aid of metallic halogen derivatives and thereby producing unstable compounds, heating the mixture at a temperature suitable for conversion action of the alkyl halide toproduce the .lower boiling compounds, distillin oil' the lower boilin compounds as formed, and returningfor urther treatment the higher boiling of the distillates while the mixture is subjected to a conversion temperature.

\ GRAYLE W. HOWLETT.

7. The process consistingxjn treating etroleum hydrocarbons with methyl chloride and Without the aid of metallic halogen derivatives and thereby producing unstable compounds, heating the mixture at a temperature suitable for conversion action of the chloride to produce the lower boiling compounds, distilling oil the lower boiling compounds as formed, and returning for further treatment the higher boiling of the distil lates while the mixture is subjected to a conversion temperat-ure.

8. The process consisting in treating petroleum hydrocarbons with an alkyl hahde and without the aid of metallic halogen derivatives applying heat and thereby produc- Ying unstable compounds, heating the mixture at a temperature suitable for conversion action of the alkyl halide to produce the lower boiling compounds, adding materials to the hydrocarbons under treatment to'maintain a substantially constant proportion and at a conversion temperature.

9. The process consising in treating petroleum hydrocarbons with an alkyl halide and without the aidof metallic halogen derivatives applying heat and thereby producing unstable compounds, heating the mixture at a temperature suitable for conversion action of the alkyl halide to produce the lower boiling compounds, adding to the petroleum hydrocarbons under treatment to take the place of the compounds removed, and maintaining the distillation at such arate that the amount of materials entering the treatment is approximately equal to the amount removed and at a conversion temperature.

10. The process of converting higher boiling petroleum oils into lower boiling .oils which comprises maintaining a boiling body of the said higher boiling oils in the presence of a non-metallic halogen derivative containing an alkyl radical and Without the aid of metallic halogen derivatives and at a temper.- ature suitable for conversion action of the halogen to produce the lower boiling compounds;

l1. The process consisting in treating pe- 

